KR920010476B1 - Bleach activation and bleaching compositions - Google Patents

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Description

Bleaching Agents and Bleaching Compositions

FIG. 1 is a graph showing theoretical ΔR (dotted line) and actual ΔR as a function of SPCC / STHOBS ratio.

2 is a graph of theoretical ΔR (dotted line) and actual ΔR as a function of the SPCC / SNOBS ratio.

FIG. 3 is a graph showing theoretical ΔR (dashed line) and actual ΔR as a function of SPCC / SNOBS ratio for Ricopan.

The present invention relates to improved bleach activator systems and bleach compositions. In particular, the present invention relates to novel bleaching and / or detergent compositions which are effective and efficient in overall bleaching performance against various kinds of contamination of fabrics or fabrics at low to medium temperatures, for example 20-50 ° C.

Detergent bleaching compositions for washing at high temperatures are well known in the art. For bleach, generally bleach includes peroxides that release hydrogen peroxide in aqueous solution, such as peroxyhydrate. These include alkali metal perborates, percarbonates, superphosphates and persilicates, urea peroxide and the like. These bleaches are effective only when the bleach solution is at a high temperature, ie only at temperatures from 80 ° C. to boiling point.

It is known that the bleaching effect of peroxide bleach compounds can be improved to be effective at low washing temperatures, for example 40-60 ° C., by using peroxy acid bleach precursors (often also called bleach activators).

Many materials have been published as effective bleaching agents in the art. U. S. Patent 836,798 (UniLever) is an example of a basic patent in the art which published such a technique. These include benzoyl esters of sodium phenol sulfonate (SBOBS) and sodium P-acetosulfonic acid salt (SABS) and several esters have been published.

Another early patent in the art is British Patent 855,735, which discloses a broad class of "acyl organamides," which are currently the most widely used N, N, N ', N'-tetraacetyl ethylenediamines. (TAED) is included.

The literature (“Detergent Age”, Allan H. Gilbert, June 1967, pages 18-20: July 30, 1967, pages 30-33: August 1967, pages 26, 27, 67) contains more various bleaching activator compounds. Is announced.

More recent patents published for bleach activators include, for example, EP-A-0 120 591, EP-1 = 0 174 132, EP-A-0 185 522 and US Pat. No. 4,412,934: 4,248,928: 4,126,573 and 4,100,095.

Typically, the material proposed and used as the bleaching agent reacts with the peroxide anion (OOH ⁻ ) of hydrogen peroxide produced by the peroxide bleach in the bleach solution to produce peroxy acid which is more reactive than peroxide bleach alone. Since it is an organic compound, bleaching is effectively performed at a bleach solution temperature of less than 60 ℃. In chemical reaction mechanisms, the effectiveness of the bleaching agent is determined by factors such as solubility, reactivity, pka, and the form of peroxy acid produced, and the performance of the bleaching agent is not equally good for different contaminations. For example, certain classes of contamination that are effectively removed by certain peroxy acid precursor-hydrogen peroxide combinations are not effectively removed by other peroxy acid precursors / H ₂ O ₂ systems. Since most of the contamination occurs in homes and workplaces, there is no single bleach activator that is effective for all kinds of bleaching and stains. Pollution in the home includes hydrophilic and hydrophobic components.

Various attempts have been made to improve the overall bleaching performance against various kinds of stains and stains on fabrics by bleach formulations, but generally have limited success or have certain deficiencies.

In addition, the trend of consistently low washing temperatures adds to the continuing need for peroxide bleach which is actually effective at temperatures of 40 ° C. and below.

EP-A-0 105 690 discloses bleach compositions consisting of peroxycarboxylic acids and aromatic sulfonyl halide bleach activators, which react to form acyl sulfonic acid as bleach. Also, a mixture of halogenated peroxybenzoic acid and a bleach activator containing carbonyl carbon atoms which react together to form diacyl and an oxide, or peroxycarboxylic acid such as diperoxydodecanedioic acid which react together to produce diacyl peroxide Bleaching compositions containing mixtures of bleach activators containing long chain acyl are disclosed in EP-A-0 106 584 (corresponding to US Pat. No. 4,671,891 to Hartman).

EP-A-0 257 700 (Unilever) discloses the use of bleach systems containing percompounds and mixtures of TAED and sodium nonanoyloxybenzene sulfonate.

EP-A-0 068 547 (Procter Gamble) discloses a laundry bleach composition containing a mixture of hydrophilic peroxy acid and hydrophobic peroxy acid bleach, representatively a mixture of perauric acid diperoxydodecanoic acid.

However, the performance of the prior art bleach systems is far from ideal. Moreover, there is no certainty about diacyl peroxides, and sulfonyl halides tend to be relatively unstable.

The present inventors have attempted to provide an improved bleaching composition which is very effective at removing various kinds of contamination, having a better background whiteness at a temperature where the bleach solution temperature is below 40 ° C.

The present inventors now have a bleaching composition comprising a peroxide bleach compound and a bleach activator system comprising a mixture of i) a hydrophobic peroxy acid bleach precursor, and ii) a cationic or amphoteric peroxy acid bleach precursor. It has been found that it has a better background whiteness at bleach solution temperature, and is very effective at removing various kinds of contamination.

One feature of the present invention therefore provides a bleach activator system consisting of a mixture of I) a hydrophobic peroxy acid bleach precursor, ii) a cationic or amphoteric peroxy acid bleach precursor and used with a peroxide bleach compound.

Another feature of the present invention provides a bleach composition comprising a bleach activator system consisting of a mixture of a peroxide bleach compound and a hydrophobic peroxy acid bleach precursor and a cationic or amphoteric peroxy bleach precursor.

The bleach compositions of the present invention are therefore materials which provide a mixture of hydrophobic peroxy acids and cationic peroxy acids when dissolved in an aqueous medium.

Each of these peroxy acids is preferably produced on its own upon dissolution, but may also be mixed into the bleach composition as the substance itself.

The present invention therefore also encompasses bleach compositions containing any one of the following mixtures.

(a) hydrophobic peroxy acid bleach precursors and cationic or amphoteric peroxy acid bleach precursors

(b) hydrophobic peroxy acid bleach precursors and cationic peroxy acids

(c) hydrophobic peroxy acids and cationic or amphoteric peroxy acid bleach precursors.

(d) hydrophobic and cationic peroxy acids

In a preferred embodiment, the bleach compositions belonging to the present invention are detergent compositions.

Like peroxy acids, they can be classified as bleach activators and have 1) hydrophilic activity or 2) hydrophobic activity or 3) intermediate activity.

Bleaching agents having hydrophilic activity (hydrophilic peroxy acid precursors) are effective against bleachable hydrophilic contamination such as tea, juice, wines and the like. Bleaching agents with hydrophobic activity (hydrophobic peroxy acid precursors) are generally derived from sebum and fatty acids / triglycerides from contamination with contact with the body, ketones and sauces including lycopene and carotene, orange pigments in tomato and spaghetti sauces. It is effective for bleachable hydrophobic contamination such as contamination.

Bleaching agents with moderate activity have both hydrophilic and hydrophobic activity, but have a narrower application range than the bleaching agents of 1) or 2).

Hydrophobic Peroxy Acid Precursor

The hydrophobic peroxy acid bleach precursor used in the present invention is in an alkaline solution containing a hydrogen peroxide source, such as a peroxide compound (e.g., sodium perborate), the parent acid of 10 g P (P) between 1.6-4.5. Is defined as a reactive organic compound having a carbonyl group capable of producing a peroxy acid having an octanol / water partition coefficient. In other words, hydrophobic peroxy acid precursors are defined as compounds which issue “peroxy acid” in the perhydrolysis, ie, in alkaline solutions containing hydrogen peroxide sources, the mother acid has a 10 g P value of 1.6-4.5. . Where P is the octanol / water partition coefficient and is:

Therefore, this is the value which measured the solubility ratio of the mother peracid in each solvent.

The hydrophobicity decreases as the 10 g P value of the mother acid decreases. Peroxy acid precursors having a 10 g P value of not more than 1.6 are unsuitable because they are too hydrophilic. The upper limit of the 10 g P value is limited only by the solubility of the precursor-peracid, and peroxy acid precursors having a 10 g P value of 4.5 or higher are not practically suitable for use.

Useful hydrophobic peroxy acid bleach precursors specified herein are compounds having the general formula:

In the above, R is a straight or branched unsubstituted or substituted C ₆ -C ₂₀ alkyl or alkylene group, substituted, unsubstituted aromatic, cyclic alkyl or heterocyclic group containing a total of 10-22 carbon atoms N is an integer between 0-1, m is an integer between 1-5, and L is a leaving group that exhibits an electron attracting effect. With a range of pka, perhydrolysine produces peroxyacids of the general formula:

Preferred hydrophobic peroxy acid precursors are those in which R is specified above in formula (I) and L is selected from:

In the above formula, R ¹ is a C ₅ -C ₁₇ alkyl group, R ² is a C _1-8 alkyl chain, R ³ is H or R ² , and Z is H or a soluble group. Z is a soluble sea component if date is _{^{-SO 3 - M +, -CO 2}} - M +, -SO 4 - M +, -N + (R 3) 3 X -, -NO -, -OH and -ON (R ² ) ₂ (wherein M ⁺ is a cation group that imparts solubility to the precursor, and X ⁻ is an anion that imparts solubility to the precursor). Among the preferred soluble groups is -SO ₃ ^- M ⁺ , where M is preferably sodium or potassium.

Particularly preferred hydrophobic peroxy acid precursors are those in which R in the formula (I) is a straight or branched C ₈ -C ₂₈ alkyl group, L is an aromatic ring, n = 0, m is 1-2. Specific examples of suitable hydrophobic peroxy acid precursors include, for example, sodium or potassium P-linear octanoyl oxybenzene sulfonate, sodium P-linear nonanoyloxy benzenesulfonate (SNOBS) or potassium, 3,5,5-trimethyl hexanoyloxy Sodium benzene sulfonate (STHOBS) or potassium, sodium 4-nonanoyloxybenzoate or potassium, 1-methoxy-2-decanoyloxybenzene-4-sodium sulfonate or potassium, 1-methoxy-2-nonanoyloxy Benzene-4-sulfonic acid sodium or potassium. Other examples of hydrophobic peroxy acid precursors are disclosed in EP-A 0 098-21 and EP-A 0 120 591.

Cationic or amphoteric peroxy acid precursors

Cationic or amphoteric peroxy acid bleach precursors are defined as bleach precursors having one or more cationic groups in their molecular structure. As such, these precursors have the general formula:

Wherein R ₁ , R ₂ , and R ₃ are unsubstituted or substituted alkyl, akenyl, alkynyl, cycloalkyl, cycloalkenyl, alkaryl, aryl, phenyl, and hydride each containing a total of 1-24 carbon atoms Oxyalkyl: a group selected from polyoxyalkylene and R ₄ OCOL, at least two of R ₁ , R ₂ , R ₃ together with the Q atoms form an unsubstituted or substituted Q-containing heterocyclic ring system; At least two of R ₁ , R ₂ , and R ₃ together with R ₄ and Q atoms form an unsubstituted or substituted Q-containing heterocyclic ring, Q is nitrogen or phosphorous, and R ₄ (R ₁ and / or R ₂ and / or heteroaryl with when R ₃ does not form a cyclic ring system) is C ₁ -C ₂₀ alkyl, alkenyl, benzyl, C ₁ -C ₂₀ alkyl optionally substituted with phenyl and aryl radicals A bridging group selected from ylene, cycloalkylene, alkylenephenylene, phenylene, arylene and polyalkoxylene, n is 0 or 1, m = 1 or 2 And, Z ^- is a chloride ion, Broome ion, hydroxide ion, nitrate soft anion, meto sulfate anion, of the sulfate anion, nitrate anion, sulfate soft anion, citrate anion, monovalent or anionic multivalent is selected from a borate anion, and phosphate anion, It can be present or omitted.

L is a leaving group having a pka of 4-13 pka, preferably 8-10, and perhydrolysis, to produce peroxy acid having the following general formula.

In particular, many of the various leaving groups structures disclosed in the literature can be used as L in the above formula (II).

For example, US Pat. Nos. 4,412,934 and 4,483,778, EP-A-170 386, EP-A-166 571 and EP-A-267 046 provide examples of preferred leaving groups.

The features of the leaving structure are selected from the following groups.

In transplantation, X ₁ and X ₂ are H or -SO ₃ ^- M ⁺ , -CCO ^- M ⁺ , -SO ₄ ^- M ⁺ , (-N ⁺ R ₁ R ₂ R ₃ ) Z ^-- NO ₂ , C ₁ Is a substituent selected from a -C ₈ alkyl group, R ₅ is a C ₁ -C ₁₂ alkyl group, R ₆ is H or R ₅ , Y is H or, -SO ₃ ^- M ⁺ , -COO ^- M ⁺ , -SO ₄ ^- M ⁺ , (N ⁺ R ₁ R ₂ R ₃ ) Z ^- or -NO ₂ . Wherein M is hydrogen, an alkali metal, ammonium or an ammonium cation substituted with alkyl or hydroxyalkyl, which may be present or omitted.

In -ONR ⁷ , NR ⁷ is succinimido, phthalimido, pyridinium, 4-phenylpyridinium or -N = C (CH ₃ ) ₂ .

특히 페놀-술폰산염 형태, 예를들면 4-술포페놀기(M⁺은 나트륨, 칼륨 도는 암모늄 양이온 염)이다.The most preferred leaving group

In particular in the form of phenol-sulfonates, for example 4-sulfophenol groups (M ⁺ is sodium, potassium or ammonium cation salts).

In formula (II), it should be recognized that the presence of (M ⁺ ) and (Z ⁻ ) as counter-ions is not essential, and compounds without these counter-ions and having amphoteric properties are also within the scope of the present invention. do.

The terms cationic and amphoteric, designated as precursor (ii), may be used interchangeably. For example

Compounds without (Z ⁻ ) and (M ⁺ ) and without quaternary ammonium and anionic soluble group substituents are also possible and can be regarded as amphoteric.

은 진정한 양이온성이다.On the other hand there is no SO ₃ ^- substituent and the same compound as the above structure, i.e.

Is true cationic.

Various cationic and amphoteric peroxy acid precursor compounds are disclosed in the literature, for example in US Pat. Nos. 4,397,757 and 4,751,015 EP-A-331,229 (January 1, 1989). Any of these precursor compounds are suitable for the present invention and some of the compounds are very preferred.

Another class of cationic peroxy acid precursors useful in the present invention is disclosed in EP-A-303 520. Suitable examples are trimethyl ammonium acetonitrile ((CH ₃ ) ₃ N ⁺ -CH ₂ -CN).

Specific examples of suitable cationic / amphoteric peroxy acid bleach precursors are as follows.

2- (N, N, N-trimethylammonium) ethyl sodium 4-sulfophenyl carbonate chloride (SPCC)

(N, N, N-trimethyl ammonium) -toluyloxybenzene sulfonate (QTOBS)

N-octyl-N, N-dimethyl-N-10-carbophenoxydecyl ammonium chloride (ODC)

N, N, N-trimethylammonium trimethylcarbonyloxybenzenesulfonate (QTCOBS)

Particularly preferred among these compounds is compound (1), ie SPCC.

[Composition]

The bleach activator system used in the present invention has an effective molar ratio of hydrophobic peroxy acid precursor (i) to cationic or amphoteric peroxy acid precursor (ii) of about 5: 1-1: 5, preferably 3: It may be composed of any of the aforementioned precursor compounds within the range of 1-1: 3.

The bleach compositions of the invention are very effective at low temperatures. The composition has excellent bleaching performance against a wide range of contaminations on fabrics, which have never been achieved with any peroxy bleach system in the art.

In comparison, the overall bleaching performance of the bleach formulations as proposed in the prior art is neither good nor poor.

Bleaching compositions containing only hydrophobic peroxyacid bleach precursors and peroxide bleach compounds or containing only cationic / amphoteric peroxyacid bleach precursors and peroxide bleach compounds do not exhibit good bleaching performance against a wide range of contaminations. .

Bleaching compositions containing only hydrophobic peroxy acid precursors have good bleaching performance at best against hydrophobic contamination such as lycopene. Bleaching compositions containing only hydrophilic peroxy acids, such as peracetic acid or its precursors (such as TAED), do not have good bleaching performance below 40 ° C, regardless of the type of contamination. Bleaching compositions containing only cationic or amphoteric peroxy acid precursors have, at best, good bleaching performance against hydrophilic contamination such as tea, wine, juices and the like.

Surprisingly, only the compositions of the present invention have truly good bleaching performance against a wide range of contaminations on fabrics and cloths at temperatures below 40 ° C. This effect is achieved by the synergistic nature, rather than simply the addition of two bleach precursors under appropriate conditions.

When mixing cationic precursors with anionic hydrophobic precursors (eg SNOBS), it is surprising that synergy is observed rather than the expected antagonistic attraction. Antagonism is expected to be due to two reasons: (i) The positive charge and hydrophobic peroxide of the quaternary ammonium peroxy acid, based on the theory that the self-decomposition of peroxy acids depends on the diffusion of two peracid molecules together. The attraction between the negative charges of the oxyacids increases the autolysis of the peroxyacids, thus reducing the bleaching. (ii) The attractive force between the positive charge of the quaternary ammonium peroxy acid and the negative charge of hydrophobic peroxy acid also causes precipitation, thus reducing the substantivity.

While not wishing to be bound by any theory, it is believed that the compositions of the present invention serve by producing and presenting two types of co-functional peroxy acids in solution:

1) with a hydrophobic peroxy acid of the general formula R (O) _n CO ₃ H

2) cationic peroxy acids of the general formula R ¹ R ² R ³ Q ⁺ -R ^4- (O) _n -CO ₃ H Thus 1) as hydrophobic peroxy acids of the general formula R (O) _n CO ₃ H Amic acid (ie R (O) _n CO ₂ H) is a hydrophobic peroxy acid having a 10 g P value of 1.6-4.5 and 2) general formula R ¹ R ² R ³ -N ⁺ -(R ₄ )-(O) _n It is within the scope of the present invention to provide a bleaching and cleaning solution containing a mixture of -CO ₃ H peroxy acids.

These cleaning and bleaching solutions are not only from compositions containing mixtures of the specific peroxy acid bleach precursors specified, but also mixtures of hydrophobic peroxy acid bleach precursors and cationic peroxy acids, hydrophobic peroxy acids and cationic or amphoteric peroxides. It can be prepared from a composition containing a mixture of oxyacid bleach precursors, or a mixture of the specified peroxy acids themselves, all within the scope of the present invention.

In all such cases the equally effective molar ratio is 5: 1-1: 5 preferably 3: 1-1: 3.

Preferred compositions contain a mixture of a hydrophobic peroxy acid bleach precursor and a cationic or amphoteric peroxy acid bleach precursor, and a mixture of hydrophobic peroxy acid and a cationic or amphoteric peroxy acid bleach precursor. Composition.

Specific examples of hydrophobic peroxy acids useful in the present invention include n-peroxynanoic acid, iso-peroxynonanoic acid and particularly preferred phthaloyl aminoperoxyhexanoic acid (PAP). PAP is a peroxy acid having the structure

This peroxy acid belongs to the class of compounds disclosed in EP-A-0 325 289.

As described above, the bleach activator system may be mixed with bleaching and / or detergent compositions which require a peroxide bleaching compound capable of producing hydrogen peroxide in an aqueous solution as an essential ingredient.

Hydrogen peroxide sources are well known in the art. This includes organic peroxide bleaching compounds such as alkali metal peroxides, urea peroxide, and inorganic peroxylate bleaching compounds such as alkali metal salts of perboric acid, percarbonate, and peracid. Mixtures of two or more of these compounds are also suitable. Preferred compounds are sodium percarbonate, sodium perborate tetrahydrate, in particular sodium perborate monohydrate. Sodium perborate monohydrate is preferred over tetrahydrate because it has excellent storage stability and dissolves very quickly in aqueous bleach solution. Rapid dissolution is believed to enable the production of large amounts of picarboxylic acid which enhances surface bleaching performance.

In general, the molar ratio of hydrogen peroxide (or peroxide compound capable of producing the corresponding amount of H ₂ O ₂ ) to the precursor is 0.5: 1 to about 20: 1, preferably 1:10 to 1: 1, more preferably. Is 2: 1-6: 1.

Detergent compositions containing peroxide compounds and the novel bleaching agent systems of the present invention also generally contain surfactants, detergent builders and other conventional ingredients added to these compositions. In such compositions, the total amount of peroxy acid bleach precursor is about 0.1-20% by weight, preferably 0.5-10% by weight, in particular 1-7.5% by weight, and the peroxide bleach compound, ie sodium perborate monohydrate or tetrahydrate. Silver is present at a level in the range of about 1-40%, more preferably about 2-30% by weight, in particular about 3-25% by weight.

The surfactant may be naturally derived, such as soap, or may be a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives, and mixtures thereof. Many suitable surfactants are commercially available and are described in detail in, for example, Surfacd Aetive Agents and detergents, Volumes I and II, Schwartz, Perry and Berch. The total amount of surfactant is 50% or less of the composition, preferably about 1-40% by weight, more preferably 4-25% by weight. Synthetic anionic surfactants are generally water soluble alkali metal salts of organosulfuric acid and sulfonic acid with alkyl radicals of about C ₈ -C ₂₂ . The term alkyl is used herein to include the alkyl portion of the higher aryl radicals. Examples of suitable synthetic anionic detergent compounds include sodium alkulfate and ammonium, in particular sodium sulfate and ammonium obtained by the sulfation of higher (C ₈ -C ₁₈ ) alcohols, for example produced from tallow or coconut oil: alkyl (C _9- ). C ₂₀ ) Sodium benzenesulfonate: Sodium alkyl glyceryl ether, especially linear secondary alkyl (C ₁₀ -C ₁₅ ) Sodium benzenesulfonate: Derived from sodium alcohol, alkylglyceryl ether, especially higher alcohols and petroleum derived from tallow or coconut oil The above ethers of synthetic alcohols: coconut oil fatty acid monoglyceride sulfuric acid and sodium sulfonate: sodium and ammonium salts of sulfate esters of higher (C ₉ -C ₁₈ ) fatty alcohol alkylene oxides (especially ethylene chloride), which are reaction products: Reaction products of the same fatty acid esterified with isethionic acid and neutralized with sodium hydroxide: fatty acid of methyltaurine Sodium and ammonium salts of de: alpha-olefins (C ₈ -C ₂₀₎ and like substances derived by the reaction of sodium bisulfite alkane mono acid salt or a paraffins and SO ₂ and by hydrolysis with a base and then reacted with Cl ₂ random Alkanesulfonates, such as substances derived from the production of sulfonates: C ₇ -C ₁₂ dialkyl sodium sulfosuccinate and ammonium: olefins (especially C ₁₀ -C ₂₀ alpha-olefins) and SO ₃ And olefin sulfonates, which refer to materials obtained by neutralizing and hydrolyzing them. Preferred anionic detergent compounds are sodium (C ₁₁ -C ₁₅ ) alkylbenzenesulfonate, sodium (C ₁₆ -C ₁₈ ) alkyl sulfate and sodium (C ₁₆ -C ₁₈ ) alkylether sulfate.

Particularly suitable nonionic surfactants used with anionic surfactants are in particular reaction products of alkylene oxides (usually ethylene oxide) with alkyl (C ₆ -C ₂₂ ) phenols (typically 5-25 units of ethylene oxide per molecule). 5-25 EO): Condensate of aliphatic (C ₈ -C ₁₈ ) primary or secondary linear or branched chain alcohol and ethylene oxide (generally 6-30 EO): Reaction product of propylene oxide and ethylenediamine and ethylene It is a product by condensation with an oxide. Other so-called nonionic surfactants include alkyl polyclicosides, long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulfoxides.

Amphoteric or zwitterionic surfactants may also be used in the compositions of the present invention, but are generally not preferred because they are relatively expensive. When amphoteric or zwitterionic detergent compounds are used, they are generally used in small amounts compared to the much more commonly used synthetic anionic and nonionic active compounds.

As mentioned above, the soap may also be mixed in the composition of the present invention, preferably in an amount of up to 25% by weight. It is particularly useful for soaps to be used in the form of bicomponent (soap / anionic) or tricomponent mixtures with nonionic compounds or mixtures of synthetic anions and nonionic compounds. The soap used is preferably the sodium or potassium salt (less preferred) or mixtures thereof of saturated or unsaturated C ₁₀ -C ₂₄ fatty acids. The amount of such soaps may vary within the range of about 0.5 to about 25 weight percent, and generally low levels of about 0.5 to about 5 weight percent are sufficient for foam control. A soap amount of about 2 to about 20% by weight, especially about 5 to about 10% by weight, is used to give an effective effect on the cleaning power. This is particularly useful for compositions used in hard water where soap acts as a supplementary builder.

In addition, the detergent composition of the present invention may typically be contained as a cleaning power builder. The builder material is selected from 1) calcium blocker 2) precipitated material 3) calcium ion exchanger 4) mixtures thereof.

Examples of calcium-blocking substances include alkali metal salts of polyphosphoric acid such as sodium tripolyphosphate: nitrilotriacetic acid and its water-soluble salts: carboxymethyloxysuccinic acid, ethirendiamine tetraacetic acid, oxydisuccinic acid, melitric acid, benzenepolycarboxylic acid , Alkali metal salts of citric acid, and polyacetal carboxylates. This is disclosed in US Pat. Nos. 4,414,226 and 4,146,495.

Examples of precipitating builder materials include sodium orthophosphate, sodium carbonate, sodium carbonate / calcite long chain fatty acid soap, and the like.

Examples of calcium ion exchange builder materials include various insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representative builder materials.

Such builder material is added, for example, in an amount of 5-80% by weight, preferably 10-60% by weight.

The detergent composition of the present invention may contain, in addition to the above-mentioned ingredients, a conventional additive in an amount conventionally used in the detergent composition for fabric washing. Examples of these additives include foam promoters such as alkanolamides (especially monoethanolamides derived from palm fatty acids and coconut fatty acids), foam inhibitors such as alkyl phosphates and silicones, sodium carboxymethylcellulose and alkyl or substituted alkyl cellulose ethers. Anti-redeposition agents, other stabilizers such as ethylene diaminetetraacetic acid and chelants based on phosphonic acid (e.g., Dequest R form), fabric softeners, inorganic salts such as sodium sulfate, etc. , Enzymes (proteases, cellulases, lipases and amylases), fungicide colorants and the like.

The bleach activator systems described herein can be used in various forms of products, including powder, sheet or gaseous products, pouches, tablets, or non-aqueous liquids such as liquid nonionic detergents. Can be incorporated.

In general, in view of stability and handleability, it is advantageous for the bleach precursor to be present in the form of particulate bodies containing the bleach precursor and a binder or flocculant. Many different methods for producing such precursor microparticles can be found in several patent documents, such as Canadian Patent No. 1,102,966, British Patent No. 1,661,333, US Patent No. 4,087,367: EP-A-0,240,057: EP-A-0,241,962: EP- A-0,101,634: published in EP-A-0,062,523. Each of these methods is optionally adapted to the bleach precursor of the invention.

Particulates containing the precursors of the present invention are generally added to the spray dried portion of the detergent composition together with other dry mix components such as enzymes, inorganic peroxygen bleach and antifoaming agents. However, the detergent composition itself to which the precursor microparticles are added may be prepared by various methods such as dry mixing, flocculation, flaking, and the like, which are well known to those skilled in the art. It does not fall within the scope of the present invention.

In addition, the bleach activator system of the present invention may be mixed in a detergent additive product. These additive products are intended to supplement or promote the performance of conventional detergent compositions, which may contain any of the components of the composition but do not contain all of the components present in a fully formulated detergent composition. Additive products according to this aspect of the invention are generally added to aqueous liquids containing a source of (alkaline) hydrogen peroxide. Under certain conditions, a source of alkaline hydrogen peroxide may be present in the product.

An additive product according to this aspect of the invention may consist solely of a compound in the form of a carrier such as a compatible particulate gas, a flexible nonparticulate gas, or a container (eg a porch or sachet).

Examples of compatible particulate gases were inert materials such as clays and other aluminosilicates including natural zeolites and synthetic zeolites. Other compatible particulate carrier materials are, for example, hydrated inorganic salts such as phosphates, carbonates, sulfates.

An additive product contained in a bag or container may be prepared in such a way that it will not release its contents when dried but will release the contents when immersed in an aqueous solution.

In another specific embodiment, the bleach activator system of the present invention is a so-called wash with peroxide bleach compounds (e.g. sodium perborate) to give effective cleaning and decontamination functions of products to fabrics and other applications. It can be mixed suitably with the aqueous non-aqueous liquid detergent composition.

Non-aqueous liquid detergent compositions, including paste-like and gelatin detergent compositions, into which the precursor compounds can be mixed, are known in the art and many compositions have been proposed. Examples include U.S. Patent Nos. 2,864,770: 2,940,938: 4,772,412, 3,368,977: GB-A-1,205,711: 1,270,040: 1,292,352: 1,370,377,2,194,536: DE-A-2,233,771, and EP-A-0,028,849.

Such compositions are generally compositions containing a non-aqueous liquid medium with or without a dispersed solid phase. The non-aqueous liquid medium is a liquid surfactant, preferably a liquid nonionic surfactant: a nonpolar liquid medium, for example liquid paraffin: a polar solvent, for example liquid paraffin: a polar solvent, for example a low molecular weight Polyols such as glycerol, sorbitol, ethylene glycol in combination with monohydric alcohols such as ethanol or isopropanol: or mixtures thereof.

Solid phases are builders, alkalines, abrasives, polymers, clays, other solid ionic surfactants, bleaches, enzymes, fluorescent agents and other conventional solid detergent components.

Essentially, the bleach compositions described herein comprise any cleaning product that requires bleaching and / or hygienic treatment (e.g., laundry detergents, laundry bleaches, household cleaners, bath tub cleaners, automatic dishwasher compositions, tooth cleaners). And the like).

The following examples illustrate the invention in more detail.

Example I

Tester contaminated with tea in a tergotometer under isothermal washing conditions at 40 ° C. for 30 minutes using a bleach solution containing hydrogen peroxide and a mixture of peroxy acid bleach precursors (i) and (ii) of varying molar ratios. The cloth was bleached. Each bleach solution was adjusted to pH 8 with H ₂ O _{2 12} mMol and total precursor concentration of 1.2 mMol.

In the first series of experiments, SPCC was used as precursor (i) and STHODS was used as precursor (ii).

In the second series of experiments, SPCC was used as precursor (i) and SNCBS was used as precursor (ii).

Bleaching performance was determined as _{ΔR 460} * for the precursor mixtures with molar ratios of 4: 0, 3: 1, 2: 2, 1: 3, 0: 4, respectively. The results are shown in FIGS. 1 and 2.

Example II

Under the same conditions as in Example I, a bleach test was conducted using SPCC / SNOBS as a precursor mixture for test cloths contaminated with lycopene.

Example III

Contaminated by car in a tagotometer under an isothermal washing condition at 40 ° C. for 30 minutes using a bleaching solution containing a system consisting of hydrogen peroxide and a cationic peroxy acid bleach precursor of hydrophobic peroxy acid PAP of varying molar ratios. The bleach test was performed on the test cloth.

Each bleach solution was H ₂ H ₂ 12mMol, total precursor / peracid concentration 1.2mMol.

In the first series of experiments, a mixture of PAP and SPCC was used in a bleach solution adjusted to pH 8. In the second series of experiments, bleach solution was adjusted to pH9 of a mixture of PAP and trimethylammonium acetonitrile (TAAN).

Bleaching performance was determined as _{ΔR 460} * for a mixture of PAP / precursors with molar ratios of 0: 4, 1: 3, 2: 2, 3: 1, 4: 0, respectively.

The results are shown in the table below.

[table]

All the above examples demonstrate that the use of a system that provides a mixture of hydrophobic peroxy acid and cationic peracid results in a bleaching effect before co-operation.

Claims (11)

(i) a hydrophobic peroxy acid bleach precursor having a log P of 1.6-4.5 (P is an octanol / water partition coefficient) and (ii) cationic or amphoteric peroxy acid bleach. A bleach activator for use with a peroxide bleach compound, consisting of a mixture of precursors, wherein the molar ratio of (i) to (ii) is 5: 1-1: 5. When dissolved in an aqueous medium. a mixture of (i) a hydrophobic peroxy acid bleach precursor having a log P of rm-1.6-4.5 (P is an octanol / water partition coefficient) and (ii) a cationic or amphoteric peroxy acid bleaching precursor. A bleaching composition provided, wherein the molar ratio of (i) to (ii) is 5: 1-1: 5. 3. A bleach composition according to claim 2 comprising a bleach activator composed of a mixture of a peroxide bleach compound and (i) a hydrophobic peroxy acid bleach precursor, and (ii) a cationic or amphoteric peroxy acid bleach precursor. Wherein the molar ratio of (i) to (ii) is 5: 1-1: 5. A bleach composition according to claim 2 which contains a mixture of hydrophobic peroxy acid and cationic or amphoteric peroxy acid bleach precursor. 4. The bleach composition of claim 3 wherein the hydrophobic peroxy acid bleach precursor has the general formula:

[Wherein R is a straight or branched C ₈ -C ₁₈ alkyl group: L is

, Wherein R ² is a C ₁ -C ₈ alkyl chain, Z is SO ₃ ^- M ⁺ and -CO ₂ ^- M ⁺ giim soluble sea component is selected from (M is being sodium or potassium): n is 0-1, m is 1-2] 6. The method of claim 5, wherein the hydrophobic peroxy acid bleach precursors include: P-linear octanoyloxybenzene sulfonate sodium and potassium: P-linear nonanoyloxybenzene sulfonate sodium and potassium; 3,5,5-trimethylhexanoyloxybenzene sodium sulfonate and potassium: 4-nonanoyloxybenzoic acid sodium and potassium: 1-methoxy-2-decanoyloxybenzenesulfonate sodium and potassium salts Bleaching composition. 4. The bleach composition of claim 3 wherein the cationic or amphoteric peroxyacid bleach precursor is 2- (N, N, N-trimethylammonium) ethyl sodium-4-sulfophenyl carbonate chloride. The bleaching composition according to claim 4, wherein the hydrophobic peroxy acid is phthaloylaminoperoxyhexanoic acid. The bleaching composition according to claim 2, wherein the molar ratio is in the range of 3: 1-1: 3. The bleaching composition according to claim 2, which also contains a surfactant. The bleaching composition according to claim 2, which also contains a cleaning power builder.

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